Production of phosphatic fertilizers



' UNITEDSTATES PATENT OFFICE rnonuc'rlon-or rnosrnn'nc rea'rmznns Beverly Cheer and Edward' H. Wight, Baltimore, Md., assignors, by mesne assignments, to The Oberphos Company, Baltimore, Md., a corporation of Maryland No Drawing. Application September 6, 1929 Serial No. 390,864

3 Claims. (Cl. 11-7) This invention relates to an improved process manufacturing phosphate fertilizer in which the of treating phosphatic material for the producseveral steps of the process, down to its preparation of phosphatic fertilizers and is a continution in a form fit for grinding, is carried out ation in part of prior applications Serial No. in a minimum of apparatus. 152,511, filed December 3, 1926, Patent 1,867,866, Yet another object is to provide a process by so July 19, 1932 and application Serial'No. 185,066, which a substantially acid free fertilizer confiled April 19, 1927, Patent 1,869,272, July 26, taining other valuable fertilizer ingredients may 1932. be produced without involving an extended cur- In the usual methods acid phosphate and douing period.

9 ble super-phosphates are prepared by reacting A further object is to provide a novel process 5 sulphuric acid or phosphoric acid with ground by which the free acid contained in mixed fertiphosphate rock. When superphosphate is to be lizers may be eliminated or neutralized while prepared the rock is ground and mixed with a incorporating additional fertilizer values. predetermined amount of acid in anopen mix- A still further object is to provide aspecial ing pan. After a very short agitation period the treatment for aprepared acid phosphate or dou- 70 charges from the pan are dumped, one upon ble superphosphate together with other fertilizer another, into a large den. In this so-called den material by whichthe free acid may be elimiprocess the reactions which begin in the mixing nated and additional fertilizer values homogenepan continue in the den, and even later, to form ously distributed through the mass.

final end products, among which are the agri- With these and other equally important ob- 75 culturally available phosphatic salts. In the jects in view the invention includes a special ordinary method the material is removed from method of treatment of phosphatic raw mathe den and'transferred to a curing shed. This terials to produce available phosphates which curing period is for the purpose of permitting a incorporates a special treatment of certain remore complete drying and lowering of the free action products so as to not only substantially an acid. eliminate free acid but also to increase the avail- In these processes the mixing period is of ability of fertilizing reaction products and to short duration and necessarily incomplete. The homogeneously incorporate additional fertilizer reaction of sulphuric acid on the tricalcium values.

phosphate and impurities is very vigorous. As In its major features the present invention a result solid end products are formed and the is quite similar to that described in the copendinitial liquid mass very soon solidifies or sets ing application above referred to but which inup. This solidification or partial solidification volvesa special treatment which is accompanied of the reactive mass prevents further agitation by decided advantages.

-5 and therefore precludes protracted mechanical In carrying out the process, predetermined 90 5 and extensive curing mixing. v quantities of phosphatic raw material, of a suit- Inthese older processes it was recognized as able degree of fineness, and a strong mineral advantageous to dust or treat the fertilizer prodacid such as sulphuric acid or phosphoric, are not with an acid absorbent such as ground phosadmitted to an autoclave. In this element the 40 phate rock or lime and to mix this with the temperatures and pressures may be so regulated 5 I .reaction products. The purpose of such a step as to retain the mass in a mixable or fluid conis to absorb or utilize the free acid which may dition for a determinative period of time, as be contained in the material. Such methods, indescribed in application Serial No. 179,706, filed volving as they do rehandling of the material 'March 30, 1927, Patent 1,837,331, Dec. 22, 1931.

periods, are uneconomical If desired, and as described in application 00 both from the standpoint of plant cost and labor Serial No. 304,789,, filed September 8, 1928, the expenditures. reactive materials may be charged to the auto- It is an object of the present invention to clave in separate streams or may be admixed devise a process for manufacturing mixed ferin a compounding stage and the resultant contilizer by which any free acid may be reduced fluent stream admitted to the autoclave. As 5 and substantially eliminated, and concomitantly described in that application, the charging may with this elimination of acid to increase the be carried out either under positively applied availability of the product and add additional pressure on the raw materials or a reduced presfertilizer values. sure on the autoclave, or by one of these meth- Another object is to provide a process for ods supplemented by the other.

While not limiting ourselves to any statement as to the physical or chemical conditions or reactions occurring in the process, it appears that the retention of pressures in the container tends to maintain substantially the initial concentration of the original elements or components of the mass and maintain sufficient water in a potentially available form for the subsequent crystallization of certain of the products.

When the reactive ingredients are charged in the manner described in application Serial No. 304,789, an intimate and substantially quantative mixture of the acid and rock dust may be obtained. However, f desired, and as noted above, the materials may be admitted to the autoclave and mixed therein while retaining high pressures. In this instance the autoclave itself, in efiect, is used as the mixing element. By retaining pressures in the container and/or cooling the materials, the reactivity of the products tends to be retarded and the mass is retained in a mixable condition for a long period of time. By agitating the material while in this substantially fluent and mixable condition a very homogeneous dispersion of the reactive components may be obtained. This, as will be appreciated, results in greater uniformity of product and higher economy of acid.

While certain methods of mixing and of admitting either mixed or unmixed materials to the autoclave are here described as the preferable methods, it is to be clearly understood that the present improvementsare by no means limited to the use of these specific preliminary steps. As will be noted hereinafter, certain of the methods of treatment embodied in the present process may be utilized to improve a fertilizer product which has already been made up by other methods.

After the materials have been thoroughly admixed in the manner described, or in any other manner, the physical conditions within the autoclave arethen regulated or adjusted so as to permit accelerated chemical reactivity and to complete the reactions which eventuate in .the desired end products. More specifically, this regulation or adjustment comprises elevating the temperature of the material within the container by any suitable means. This increase in temperature accelerates the reaction and permits the conversion of the insoluble phosphates to the soluble form. The reaction may be further speeded up by diminishing the pressure slightly. If desired, both the temperature and pressure conditions may be adjusted so as to insure a speedy reaction.

It will be understood at this point that the pressures utilized in the system may be autogenous or may be generated from some extraneous source. In. the treatment of the ordinary type of phosphatic raw material, namely tricalcium phosphates, the character of the impurities in the rock are such as will generate a sufficient amount of vapors and of gases to supply the desired pressures. However, it is to be clearly understood that if desired the material may be placed under the pressure of an inert gas admitted from an extraneous source. Also steam may be forced into the autoclave to maintain the pressure. This method of creating a pressure is of particular advantage, since it affords an artificial vapor tension and thus assists in the maintenance of the water in the reaction mass. After the materials have been mixed,

either by the process described in application 304,789, or in application 179,706 Patent 1,837,- 331, Dec. 22, 1931, the conditions are adjusted to insure the complete reaction of the reactive components. During the reaction stage the acid continues to react on the unattacked rock to convert the tricalcium phosphate into mono or dicalcium phosphate.

After the material has been permitted to digest for a requisite periodof time, the conditions in the container are then adjusted to permit the crystallization of the ,product. As pointed out in the copending application, this may be done by releasing the pressure within the container. Upon release of pressure there is a sudden drop in the internal temperature due to the exit of gases and moisture vapor. This diminution in temperature tends to aid in crystallization of the crystallizable components of the product. The final product, as. is known, contains crystalline salts such as mono and dicalcium phosphate, which take on water of crystallization. Due to the conditions under which the reaction was carried out, namely in a closed container in which components were maintained, the reactive zone contains suflicient water to completely crytallize the mass.

The product obtained from this treatment contains water soluble and citrate soluble phosphates and certain unavailables such as calcium sulphate or phosphate. In addition to this, and particularly if the digestion has been incomplete or the mixinghas not been carried out under optimum conditions, as for example in employing the old processes of mixing, the material may contain some quantity of free acid. The present invention contemplates mixing materials having fertilizer value with the products of conversion to form fertilizers having certain desired properties. When it is desired to form a mixed phosphatic nitrogen fertilizer a nitrogenous material may be added thereto. This may include ammonium sulphate, ammonium, or sodium nitrate, hair, wool, feathers, leather, fur, fish scrap, garbage, cyanamid and other nitrogen bearing material. In place of the nitrogenous material or together therewith suitable potash-containing material may be added. The latter may be in the form of potassium salts or other compounds containing agriculturally available potassium.

The material having the additional fertilizer value is added when the action of the acid on the phosphatic material has run to completion. The presence of free acid has disadvantages. The acid renders the material damp and gummy and its presence in the older processes necessitated such expedients as dusting with raw phosphate rock and subjecting it to curing, aeration or remilling. As a general rule it was necessary to first dust the product under careful conditions because the presence of the liquid acid prevented any great handling of the material due to its tendency to gum or become muddy. Furthermore the strong acid tends to rot the bag or other container in which the material is packed.

Now according to the present invention, any free acid in the fertilizer mixture is neutralized by an expeditious method which serves in addition to impart other valuable properties to the material. Briefly considered this method consists in adding a predetermined quantity of ammonia so as not only to kill any free acid, but

also to form compounds having fertilizer value. 1

' method about to be opened. The then existing pressure It is to be understood that the reduction of free acid and the addition of fertilizer values, and the increase in the availability of the product, all of which functions are subserved by the described, applies equally whether the method is employed on a product prepared by autoclaving as described herein, or or as set forth in application Serial No. 304.789, filed Sept. 8, 1928, or on a product produced by the usual den process. It is to be understood, therefore, that while the step is described as being particularly advantageous when used in conjunction with the prior autoclaving, it is nevertheless available for. treatment of any fertilizer product which may contain acid constituents which are to be neutralized, or the fertilizer value of which is to be increased.

According to the present method, after the digesting period has been completed and the additional material added, the vacuum 'pump is operated so as to place the material-under a vacuum. When the desired vacuum has been obtained a neutralizing substance which will kill the free acid and/or react with certain of the compounds in the product to produce'other components having fertilizer values is added. A very desirable material for this use is ammonia. This may be added in any suitable manner and in any physical condition. For example it may be added as ammonia gas, anhydrous ammonia or aqueous ammonia.

Assuming that aqueous ammonia is to be used, the autoclaveis connected to the ammonia tank. When the material in the autoclave has been placed under a vacuum the valve connecting the ammonia tank and the autoclave is differential causes a strong influx of ammonia into the autoclave. Now during the admission of the ammonia and in fact during the entire ammonification process, the autoclave is rotated and subjected to a cooling action such as contemplated in the process set forth in copending application 166,808, filed February 8, 1927 Patent 1,837,307 Dec. 22, 1931. The reasons for this are as follows: When ammonia is mixed with an acid phosphate product, certain exothermic actions follow and a considerable amount of heat is generated. This rise in temperature presents certain disadvantages. In the first place it tends to vaporize the water in the mass and render the latter unavailable for the crystallization of the products.

Furthermore it appears that by maintaining the mixture in a cool condition, increasing amounts of ammonia may be absorbed, with decreasing reversion in availability of the superphosphate. In any event we find that it is highly desirable to maintain the material in a relatively cool condition and at least to the extent of largely abstracting the exothermic heats of reaction. Our invention therefore comprehends any and all means and methods by which the temperature'of the mass may be controlled during the ammonification process.

A second and very important factor in' ammonification is the control of the surface area. We have found that it is desirable to have the solid products charged and ammonified in as disperse or discrete a condition as possible. The reason for this appears to be two-fold. With a small subdivision of the phosphate acceleration of the ammonification by reason of the fact that greater surface area is exposed to the action of the ammonia containing substance.

there is an Furthermore by maintaining the phosphatic material in a finely divided condition there is a greater distribution and homogenity of the reaction products of ammonia and local concentration. In order to obtain the optimum surface exposure conditions we may reduce the material to finely divided form. This may be done either by rotating the autoclave itself so as to break up or tend to break up the phosphatic and other material, or by placing in the autoclave a means which will subserve a grinding function. If desired, also the material may be withdrawn from the autoclave in which it is first treated and subjected to a grinding action so as to increase the surface area after which it may be admitted to a second autoclave and, after a reduction of pressure, ammonia may be admitted into the zone of reduced pressure.

A peculiar advantage of utilizing a reduced pressure or vacuum on the material to which the ammonia is to be introduced is the fact that this reduced pressure tends to draw in the ammonia liquid as a gas. This of course tends to a wide diminution of the ammonia through the material which is to be treated. Furthermore we have found that this distribution is substantially continuous throughout the introduction of the ammonia. This appears to be due to the avidity of the neutralent for the material within the container when the optimum reactive conditions are provided as explained.

The affinity of the ammonia for the phosphate material results in the chemical combination of the ammonia to produce ammonium sulphate salts, ammonium phosphate salts and/or other complex sulphates, phosphates, or possibly ammonium fluoride compounds, and hence any tendency to the increase of pressure due to the admission of gas is eliminated.

Inasmuch as the increase in the surface area tends to a more homogeneous or holosteric product with a diminution in the time of reaction, we may employ other means to enhance this result. For example, not only may we grind the product to increase the surface exposure, but we may also mix the phosphatic material with spreading material, such for example as sawdust. At this point it should be noted that the substance containing the additional fertilizer value plays the part of a spreading agent.

As notedabove, whether the material is ammonified in the container in which it is prepared or whether the material which is ammonified is that prepared by the den method, we contemplate agitating the mass fication. This may readily be done in the present case by rotating the autoclave. This rotation serves, so to speak, to-circulate the reactive components and to insure a more even distribution and/or concentration of the reaction materials. In this manner particles of the phosphatic and other material are continuously subjected to contact with the ammonia containing substance with the resulting increase in reaction speed and homogeneity of reaction products.

In employing the autoclave hereinbefore described the agitation of the mass may be carried on simultaneously'with the cooling. The provision of an external cooled jacket enables the temperature of the mass to be controlled so as to provide optimum reaction conditions for ammonia absorption and thereby prevent heterogeneity and reversion. Obviously, however, in stead of using an autoclave with an external shell we may provide other cooling means. For 150 less danger of during ammoniexample we may insert a cooling coil in the interior of the autoclave, or we may utilize the expansion of anhydrous ammonia, in a suitable apparatus, to utilize its well known refrigerating effect. This and other equivalent means of controlling the temperature during ammonification are contemplated herein.

After the ammonification process the material may immediately be removed. It will be noted that due to the provision of controlling the temperatures during the process the material may be removed in a relatively cool state. The material may then be put through a grinding machine if desired, although when the product has been put through a grinding machine prior to the ammonification, a second grinding after ammonification is never necessary. It will be noted that the product is in excellent physical condition for grinding, packing and use. Due to the conditions under which the ammonification is carried out, the material comprises phosphatic, nitrogenous and/or potassium com pounds having fertilizer values which are intimately and homogeneously dispersed through the mass. Due to the control of the temperature during ammonification and to the controlled amount of ammonia added, the material contains substantially no free acid and a minima! amount of water.

As noted hereinbefore the improvements described herein are applicable not only to a material produced by a novel method of autoclaving but also to any mixed phosphatic fertilizer product, as for example a product prepared according to the usual den method. In operating on-a den product the material may first be ground, admitted to an autoclave, the pressure reduced therein and the ammonia introduced into the zone of reduced pressure. In this case, it will be appreciated, the reduced pressure zone within the autoclave serves as the suction means for drawing in the ammonia and furthermore insures uniform' contact of the reaction materials.

In operating with an autoclave process the ammonification may be carried out either in the autoclave in which the digestion is done or in a separate autoclave. The separate autoclave presents some advantages. The element itself, when used only for ammonification, need not be as expensive because it is not subjected to the rigorous high pressure conditions of the digester. Furthermore by using a separate autoclave for the ammonification step it is possible to obtain operating economies, as for example by using a single ammonification autoclave for a plurality of digesters. In any and all of these cases it will be noted that the salient features of the invention include the introduction of ammonia to and in contact with' the fertilizer product, which latter is maintained under a reduced pressure, the'reaction of absorption of the neutralent such as ammonia under conditions of optimum surface area is obtained for example by fine grinding or by the use of spreading materials, or by the use of agitation or any combination of these steps. Of course, in each of the several methods of ammoniating the fertilizer, suitable methods and means for absorbing the heat generated may be-employed to secure products having the desired properties.

It will be appreciated that we have provided a process for the treatment of materials whereby these materials may easily and expeditiously be treated to produce an improved product.

While we have described preferred embodiments of the invention, it is to be understood that these are given as typical and' are to be considered as exemplifying the principles of the invention and not as restricting them to any stated number and sequence of steps or choice of particular materials.

We claim:

l. The process of producing fertilizers com- .prising converting phosphate rock to available forms by digesting the rock with an acid under superatmospheric pressure, agitating the products of digestion with other material having a fertilizing value, reducing the pressure thereon, then adding ammonia while subjecting the mass to agitation and cooling.

2. The process of improving fertilizers comprising digesting the ground phosphate rock with sulphuric acid in an autoclave under superatmospheric pressure, adding to the products of digestion other material having a fertilizing value, reducing the pressure on the material below atmospheric, agitating the mixture of materials in the autoclave and admitting ammonia thereto and maintaining the temperature below a point which tends to detrimentally affect the product.

3. The process of preparing fertilizers comprising reducing phosphate rock to a state-of fine subdivision, subjecting the material at elevated temperatures and in a confined space to the action of an acid, agitating the mixture during digestion, mixing the product with other material having a fertilizing value, reducing the pressure below atmospheric and adding thereto material having combinab'le ammonia and agitating and cooling the material during the addition of the ammonia-containing material.

BEVERLY OBER. EDWARD H. WIGHT. 

